1, 12-di-beta-cyanoethoxy-9-octadecene and method of preparation



United States Fatent 3,671,611 1,l2-DI-BETA-CYANOETHQXY-9-0CTADECENE AND METHOD F PREPARATIGN Harold P. Dupuy, Leo A. Goidblatt, and Frank C. Magne,

New firleans, La., assignors to the United States of America as represented by the Secretary or Agriculture No Drawing. Appiication Nov. 18, 1959, Ser. No.

859,831, new Patent No. 3,052,680, dated Sept. 4, 1962,

which is a division of application Ser. No. 786,661,

.ian 13, 1959, now Patent No. 2,971,355, dated Feb. 14,

1%}. Divided and this application Feb. 2, 1962, Ser. No. 17,83tl

l Ciaim. (ill. 260--465.6)

(Granted under Title 35, [1.5. Code (E52), sec. 266) A non-exclusive, irrevocable, royalty-free license in the invention herein described, throughout the World for all purposes of the United States Government, with the power to grant sublicenses for such purposes, is hereby granted to the Government of the United States of America.

This application is a division of application Serial No. 859,831, filed November 18, 1959, now Patent No. 3,052,680, which is a division of application Serial No. 786,661, filed January 13, 1959, now Patent No. 2,971,855.

This invention relates to nitrogen-containing derivatives of ricinoleic acid. More particularly, this invention relates to the morpholides and cyanoethylated derivatives of ricinoleic acid and its derivatives. These nitrogencontaining compounds have utility as plasticizers for both vinyl chloride polymers and for cellulose esters.

Ricinoleic acid is a unique fatty acid found in castor oil in the form of an ester of glycerol. Ricinoleic acid normally comprises about 90% of the fatty acids present, as glycerides, in castor oil. Chemically, ricinoleic acid is l2-hydroxyoleic acid or 12-hydroxy-9-cctadecenoic acid which may be represented by the following formula:

A morpholide of an acid is an amide of the acid in which the amido nitrogen atom is a nitrogen atom of a morpholine ring. Prior workers have produced the morpholides and other amides of some of the more common fatty acids. The morpholides have generally been prepared by the reaction of morpholine with acid chlorides, acids, or acid anhydrides.

Cyanoethylated derivatives are conventionally produced by vinyl addition of acrylonitrile (CH =CHCN) to reactive hydrogen atoms contained in alcohols, phenols, and the like compounds. Each reactive hydrogen atom causes a vinyl group of the acrylonitrile to become saturated, thus producing cyanoethylated derivatives having beta-substituted propionitrile groups attached via ether linkages. The cyanoethylation reaction has been applied in the prior art to a large number of monohydric and polyhydric alcohols, as Well as to numerous other compounds having reactive hydrogen atoms.

A primary object of the present invention is to provide processes for producing new morpholides and cyanoethylated derivatives of ricinoleic acid and its derivatives. A further object is to produce novel nitrogen-containing plasticizers from ricinoleic acid and its derivatives, said plasticizers being suitable for plasticizing either vinyl chloride polymers or cellulose esters. Other objects will be apparent from the description of the invention.

In general, according to this invention, the esters of ricinoleic acid and of its derivatives are reacted with morpholine to produce the morpholides. It is generally preferred to use the methyl esters for this ammonolysis reaction, although other esters such as ethyl esters, propyl esters etc. may also be employed. When the preferred methyl esters are subjected to the ammonolysis reaction 7 with morpholine, the hydrogen atom of the secondary amine structure of the morpholine combines With the methoxyl group of the ester to yield methyl alcohol and the morpholide, according to the following equation:

CHI-CH2 CED-OH:

CHz-CHz CHr-CH: where R represents an alkyl or alkenyl group having an alcoholic hydroxyl substituent. The hydroxyl group can either be left free and unreacted, or it can be made to react with any of the reactants commonly used for reacting with alcoholic hydroxyl groups.

Suitable methyl ester reacants include: methyl ricinoleate; methyl 12-hydroxystearate; methyl ricinolaidate; and the like. Suitable reactants for introducing substituents on the hydroxyl groups of the morpholides include acetic anhydride for making acetoxy derivatives, acrylonitrile for making cyanoethylated derivatives, and the like reagents commonly used for reacting with alcoholic hydroxyl groups.

The reaction for preparation of morpholides according to this invention proceeds smoothly at relatively moderate temperatures in the absence of a catalyst. The morpholides can be obtained in substantially quantitative yield simply by refluxing the methyl esters with morpholine, while at the same time distilling off the methyl alcohol as it is formed in the reaction. This is the preferred procedure. Since the distillation temperature of methyl al- Gohol is quite low as compared to that of morpholine, efficient fractionation is not required and relatively little of the morpholine distills over with the methanol during the course of the reaction. The progress of the reaction can be followed conveniently by observing the rise in relfux temperature or more accurately by titrating aliquots of the reaction mixture to ascertain the quantity of unrecated morpholine remaining.

It is generally preferred to carry out the reaction at a temperature at least as high as the reflux temperature of the particular mixture of reactants being employed. Temperatures considerably lower than this are not generally suitable, since the rate of reaction becomes too slow to be practical. Extremely high temperatures are not desirable, especially when unsaturated methyl ester reactants are used, since there is danger of degradation, modification, or decomposition of the reactants.

While the morpholine and the ester reactants combine in a 1:1 ratio, it is usually preferred to employ an excess of morpholine. About 2 moles of morpholine for each mole of ester is particularly suitable.

The length of reaction time can be controlled depending on the particular reactants being employed and the extent of conversion desired by the operator. Essentially complete conversion to the morpholide is usually achieved in about 36 hours under the preferred conditions.

Although suitable unreactive solvents for the reactants can be used in the reaction mixture, it is not generally desirable or advantageous to employ such solvents. The morpholihe and ester reactants are mutually soluble and provide a homogeneous reaction mixture without the incorporation of a solvent.

The isolation and recovery of the morpholide product can be accomplished without difficulty. At the end of the reaction period, the excess morpholine is removed, preferably by distillation at a pressure below normal atmospheric pressure. The morpholide product remaining can be used without further purification, or it can be purified by conventional means. Distillation, solvent crystallization, and the like are generally preferred means for purify- Water is preferred, in view of the fact that it is an ecoing the morpholides. nomical and effective polymerization inhibitor. When The unreacted hydroxyl group of the morpholide produsing water, we prefer to use about 0.1 part by weight of ucts of the present invention can be acylated with the usual inhibitor for each part by weight of reactant being cyanoacylating agents under the conditions conventionally em- 5 ethylated. ployed for acylations. For example, unique acetoxy de- While temperatures ranging from about room temperarivatives can be prepared by treating said morpholides ture to the decomposition temperature of the reactants can with acetic anhydride. It is generally preferred to use an be used, maximum temperatures of from about 70 C. to excess of acetic anhydride and heat the reaction mixture about 85 C. are particularly suitable for employment in to a temperature below the decomposition temperature of the cyanoethylation process of the present invention. A the reactants during the acylation. It is convenient to preferred procedure is to add the acrylonitrile to the reacemploy about 1 part by weight of the acetic anhydride for tion mixture at such a rate that as the reaction proceeds each part by weightof morpholide, and to carry out the the temperature of the mixture gradually rises to the preacylation reaction at the reflux temperature of the reaction ferred maximum reaction temperature (about 70 C. to mixture until the desired extent of reaction is obtained. 85 C.). Following complete addition of the acrylonitrile, The acetoxy derivative is readily isolated by means of the reaction mixture is maintained at the said preferred distillation or other conventional procedures. maximum reaction temperature a sufficient length of time In preparing cyanoethylated derivatives of ricinoleic until the desired extent of cyanoethylation is achieved. acid derivatives according to the process of the present From about 50% to about 80% conversion to cyanoinvention, acrylonitrile is reacted with the reactive hydroethylated product is achieved in about 3 to 4 hours under gen atoms of the alcoholic hydroxyl groups of the ricinthe preferred reaction conditions. The cyanoethylated oleic acid derivatives. The cyanoethylated products conproduct can be isolated and recovered without difficulty tain beta-substituted propionitrile groups attached by by employing conventional procedures such as phasic means of ether linkages. For example, when 4-ricinseparations, distillations, crystallization from solvents and oleoylmorpholine is the reactant being cyanoethylated the the like. reaction can be represented by the following equation: The nitrogen-containing derivatives of the present in- GHQ-CH2 (H) 11 0\ N-C(OHz)r-CH=CHCHz-( (CHz)sOH CHa=CHCN CHz-CHz H CHr-CH: O H I E O\ N-C-(CH2)1-CH=CHCH2- --(CH2)5CH:

CHI-0H2 6 (iiHzQHaCN Suitable reactants which can be cyanoethylated include: vention have unique plasticizing properties. They exhibit 4-ricinoleoylmorpholine; 4-(12-hydroxystearoyl)-morphogood compatibility with polymers and copolymers of line; ricinoleyl alcohol; and the like. When ricinoleyl monomers predominating in vinyl chloride, such as polyalcohol is used as the reactant, both of the alcoholic hyvinyl chloride, and the vinyl chloride-vinyl acetate codroxyl groups of said reactant are cyanoethylated to yield polymers predominating in vinyl chloride. They can be the di-cyanoethoxy compound, namely 1,12-di-beta-cyanoemployed as plasticizers in pro-portions of from about 10 ethoxy-9-octadecene. to 80 parts by weight per 100 parts by weight of polymer.

The cyanoethylation reaction proceeds readily at mod- In addition, some of the nitrogen-containing derivatives crate temperatures in the presence of an alkaline catalyst. are likewise suitable as plasticizers for cellulose esters, Any of the conventional alkaline catalysts, such as metallic such as cellulose acetate. They can usually be employed sodium or potassium (producing the corresponding alkin proportions of up to about 40 parts by weight per 100 oxides) may be used. We prefer to employ a quaternary parts by weight of cellulose acetate and still exhibit good amine base type catalyst, such as benzyltrimethylamcompatibility. The suitability of the nitrogen containing momum hydroxide and the like. The concentration of derivatives of this invention as plasticizers for two such catalyst in the reaction mixture can be varied widely. widely different types of materials is unique. About 0.04 part by weight of quaternary amine for 1 part The following examples are given by way of illustraby weight of reactant being cyanoethylated is particularly tion and not by way of limitation of the invention. suitable.

It is generally preferred to conduct the reaction in a EXAMPLE 1 suitable solvent medium. Any solvent in which the re- A mixture of 312 grams (1 mole) of methyl ricinoleate actants are soluble and which is unreactive toward the rea 174 grams (2 moles) of morpholine was heated in a actants is generally suitable. Dioxane is a particularly reaction flask under gentle reflux for about 36 hours.

suitable solvent. The quantity of solvent employed can The methyl alcohol produced during the course of the be varied widely, but about 1 part by'weight of solvent for reaction was allowed to distill out of the reaction flask each part by weight of reactant being cyanoethylated is through a short Vigreux column and condensed in a usually preferred. Dean-Stark trap. During the 36 hour reaction period, the

The relative amounts of ricinoleic acid derivative and reaction temperature gradually rose from 145 to 180 C. acrylonitrile in the reaction mixture can be varied widely. and approximately 1 mole of methyl alcohol was evolved. However, since these two reactants combine in a 1:1 ratio At the end of the reaction period, the unreacted morfor each hydroxyl group undergoing cyanoethylation, it is pholine was removed by distillation under vacuum. The desirable to assure at least this theoretical ratio in the reaction product was distilled, yielding 320 grams of matereaction mixture. An excess of acrylonitrile is usually rial distilling at 243-246 C. at 0.2 millimeter: N preferred. About 2 moles of acrylonitrile for each mole 1.4891; d 0.9756; [0:1 4.38. The purified product of hydroxyl group in the reactant being cyanoethylated is contained 71.47% carbon, 11.02% hydrogen, 3.80%

particularly suitable. nitrogen, and 4.68% hydroxyl, as determined by conven- The use of a polymerization inhibitor in the reaction tional analytical procedures. The product was thus mixture is des1rable. Otherwise, an excessive amount of shown to be 4-ricinoleoylmorpholine which has a theoretithe acrylonitrile will polymerize to form polyacrylonitrile cal content of 71.88% carbon, 11.24% hydrogen, 3.81% and thus be unavailable for the cyanoethylation reaction. nitrogen and 4.63% hydroxyl.

The compatibility of the plasticizers with the vinyl chlo ride polymers in all of the examples was determined on the basis that exudation or bleeding out of the plasticizer within 15 days was poor," and a lack of bleeding for at least 45 days was good.

The 4-ricinoleoylmorpholine was also tested as a plasticizer for cellulose acetate. Thirty parts by weight of plasticizer and 100 parts by weight of cellulose acetate (40% acetyl content) were dissolved in acetone, and cast films were prepared from the acetone solution by allowing the solvent to evaporate slowly from portions of the solution placed in shallow dishes. The films were stripped from the dishes, heated 1 hour at 80 C., and examined. The films were dry and clear, indicating compatibility of the plasticizer with the cellulose acetate.

EXAMPLE 2 One part by Weight of the 4-ricinoleoylmorpholine of Example 1 was refluxed with 1 part by weight of acetic anhydride for about 2 hours. The acetic acid and excess acetic anhydride were then removed from the reaction mixture by distillation under vacuum. The acetoxy derivative was purified by distillation at 0.2 millimeters pressure, its distillation temperature being 230234 C. at this pressure. The purified product had the following characteristics: N 1.4789; (1 0.9836; [ch 20.35. It was found to contain 69.99% carbon, 10.53% hydrogen, 3.24% nitrogen and hydroxyl. The product was thus shown to be 4-(12-acetoxyoleoyl)morpholine which has a theoretical content of 70.37% carbon, 10.58% hydrogen, 3.42% nitrogen, and 0% hydroxyl.

The 4-(l2-acetoxyoleoyl) morpholine was compared with DOP in the standard formulation described in Example 1. Th results are given in Table II.

Table II Tensile 100% Elonga- Brittle Gompati- Strength, Modulus, tion, Per- Point, bility p.s.i. p.s.i. cent C.

4-(12-acetoxyole Good. 2, 990 1, 370 340 -23 oyl)m0rpholine. DOP Go0d 3,000 1,650 320 31 The 4-(12-acetoxyoleoyl) morpholine was tested as a plasticizer for cellulose acetate (40% acetyl) as described in Example 1. Good compatibility was obtained using either thirty or forty parts by weight of plasticizer per 100 parts by weight of cellulose acetate.

EXAMPLE 3 6 commercial hexane contained 71.53% carbon, 11.79% hydrogen, 3.75% nitrogen, and 4.59% hydroxyl. The product was thus shown to be 4-(l2-hydroxystearoyl)- morpholine which as a theoretical content of 71.49% carbon, 11.73% hydrogen, 3.79% nitrogen, and 4.60% hydroxyl.

EXAMPLE 4 One part 'by weight of the 4-(12-hydroxystearoyl)- morpholin of Example 3 was refluxed with 1 part by weight of acetic anhydride for about 2 hours. The acetic acid and excess acetic anhydride were then removed by vacuum distillation. The reaction product was purified by distillation at 0.2 millimeter pressure, its distillation temperature being 234235 C. at this pressure. The purified product had the following characteristics: N 1.4709; 11 0.9726. It was found to contain 69.62% carbon, 11.17% hydrogen, 3.24% nitrogen, and 0% hydroxyl. The product was thus shown to be 4-(12- acetoxystearoyl)rnorpholine which has a theoretical content of 70.03% carbon, 11.02% hydrogen, 3.40% nitrogen, and 0% hydroxyl.

The 4-(l2-acetoxystearoyl)morpholine was compared with DOP in the standard formulation described in Example 1. The results are given in Table III.

Table III Tensile Strength,

p.s.i.

Elon ation, Per cent 100% Brittle Modulus Point,

p .s.i. 0.

Compatibility 4-(12-acetoxystearoyl)morpholine. DOP

Good... 2, 980 1, 510 303 -21 Good- 3, 000 1, 650 320 -31 EXAMPLES 5 EXAMPLE 6 368 grams (1 mole) of the 4-ricirroleoylrnorpholine of Example 1 was dissolved in 368 grams of dioxane. To this solution was added 37 milliliters of water as a polymerization inhibitor and 37 milliliters of Triton B (a 40% by weight solution of benzyltrimethylammonium hydroxide in methyl alcohol) as catalyst. Two moles (106 grams) of acrylonitrile was then added dropwise to the mixture with stirring during a 30-minute period, during which time the temperature rose to about C. The reaction mixture was stirred and maintained at about 75 C. for three additional hours, and was poured while still warm into 3 liters of diethyl ether. The solution was allowed to stand a few hours to precipitate most of the polyacrylonitrile. The ethereal solution was decanted from the precipitate, filtered, and the filtrate was neutralized with dilute aqueous hydrochloric acid and then Washed free of excess acid with water. The resulting ethereal layer was vacuum distilled to remove ether, and then distilled rapidly under high vacuum to isolate the cyanoethylated product. The fraction which distilled at 248254 C. at 20 microns pressure was purified by crystallization from 15 volumes of methyl alcohol at 70 C. overnight. The purified product had the following characteristics: N 1.4816;

(113 141.20 It was found to contain 70.74% carbon, 10.40% hydro- 7 gen, and 6.64% nitrogen. The product was thus shown to be 4-(1Z-beta-cyanoethoxyoleoyl)morpholine which has a theoretical content of 71.38% carbon, 10.54% hydrogen, and 6.66% nitrogen.

The 4-(l2-beta-cyanoethoxyoleoyl)morpholine was compared with DOP in the standard formulation described in Example 1. The results are given in Table IV.

EXAMPLE 7 370 grams (1 mole) of the 4-(12-hydroxystearoyl)- morpholine of Example 3 was cyanoethylated with 106 grams (2 moles) of acrylonitrile in the same manner and under the same conditions as described in Example 6. In this case, the acrylonitrile was added during a -minute period and the temperature of the reaction mixture rose to about 80 C. The mixture was then sirred and maintained at 70 C. for three additional hours. The reaction mixture was further processed as described in Example 6. The fraction of the reaction product which distilled at 246-252 C. at microns pressure was purified by crystallization from 10 volumes of acetone at 25 C. overnight to precipitate noncyanoethylated morpholide. Acetone was removed from the resulting filtrate by vacuum distillation to obtain the cyanoethylated morpholide. It was recrystallized from 15 volumes of methyl alcohol at 70 C. overnight. The recrystallized product contained 70.85% carbon, 10.85% hydrogen, and 6.55% nitrogen. The product was thus shown to be 4-(1Z-beta-cyanoethoxystearoyl)- morpholine which has a theoretical content of 71.04% carbon, 10.97% hydrogen, and 6.63% nitrogen.

The 4-(12-beta-cyanoethoxystearoyl)morpholine was compared with D0? in the standard formulation described in Example 1. The compatibility of the 4-(12- beta-cyanoethoxystearoyl)morpholine was good. Its percent elongation was 380% as compared to 320% for DOP, and its tensile strength was 3120 psi. as compared to 3000 p.s.i. for DOP.

8 EXAMPLE 8 1284 grams (1 mole) of ricinoleyl alcohol was dissolved in 284 grams of dioxane. To this solution was added 28 milliliters of water as a polymerization inhibitor and 28 milliliters of Triton B (a by weight solution of benzyltrimethylammonium hydroxide in methyl alcohol) as catalyst. Four moles (212 grams) of acrylonitrile was then added dropwise to the mixture with stirring during a 1-hour period, during which time the temperature rose to about C. The reaction mixture was stirred and maintained at about 70 C. for three additional hours, and was poured while still Warm into 3 liters of diethyl ether. The solution was allowed to stand a few hours to precipitate most of the polyacrylonitrile. The ethereal solution was decanted from the pre cipitate and the ether was removed from the solution by vacuum distillation. The residue was distilled rapidly under high vacuum. The fraction which distilled at 228-238 C. at 25 microns pressure was crystallized from 15 volumes of methanol at 70 C. overnight. The purified product had the following characteristics: N 1.4632;

afg 14.30

It was found to contain 74.20% carbon, 11.18% hydrogen, and 7.08% nitrogen. The product was thus shown to be 1,1Z-di-beta-cyan-oethoxy-9-octadecene which has a theoretical content of 73.79% carbon, 10.84% hydrogen, and 7.17% nitrogen.

The 1,12-di-beta-cyanoethoxy-Q-octadecene was compared with DOP in the standard formulation described in Example 1. The results are given in Table V.

1,12-di-beta-cyanoethoxy-9-octadecene.

No references cited. 

